2,2-dimethyl-6-(n-propyl)-4H-1,3-dioxin-4-one | 95395-79-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyl-6-(n-propyl)-4H-1,3-dioxin-4-one
• 英文别名: 2,2-Dimethyl-6-propyl-1,3-dioxin-4-one；2,2-dimethyl-6-propyl-2H,4H-1,3-dioxin-4-one；2,2-dimethyl-6-propyl-1,3-dioxin-4(2H)-one；2,2-dimethyl-6-propyl-4H-1,3-dioxin-4-one
• CAS: 95395-79-2
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: QILPFEZTOOEGFL-UHFFFAOYSA-N

物化性质

• 沸点：
  55-56 °C(Press: 0.08 Torr)
• 密度：
  1.008±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-6-(n-propyl)-4H-1,3-dioxin-4-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 Methyl (S)-2,5-Dihydro-3-hydroxy-5-oxo-4-(1-oxobutyl)furan-2-ylacetate
  参考文献：
  名称：

  Synthesis of 1,3-dioxin-4-ones and their use in synthesis. Part XXII. A novel synthetic method for tetronic acids from 1,3-dioxin-4-ones via intra- or intermolecular ketene trapping.

  摘要：

  本文介绍了从 6-取代的 1,3-二恶英-4-酮通过环己基转化为酰基烯烃，然后通过羟基功能进行分子内或分子间酮阱合成四烯酸及其衍生物的新合成路线。四烯酸及其 5-取代衍生物是通过分子内捕集法从 6-（x-羟基烷基）-1, 3-二恶英-4-酮直接合成的，而 3-酰基四烯酸则是通过分子间捕集法使从 6-取代的二恶英酮中获得的 β-酮酯和适当的 α-羟基酯发生迪克曼反应而制备的。

  DOI：

  10.1248/cpb.38.94
• 作为产物：
  描述：

  丁酰乙酸乙酯 在 硫酸 、 乙酸酐 、 sodium hydroxide 作用下， 以 水 为溶剂， 反应 5.0h， 生成 2,2-dimethyl-6-(n-propyl)-4H-1,3-dioxin-4-one
  参考文献：
  名称：

  One-Pot, Diversity-Oriented Synthesis of Aryl-Substituted Benzoxacycles Including Benzofuran, Coumarin, and Benzoxazepine

  摘要：

  A one-pot method for the synthesis of benzoxacycles including benzofuran, coumarin, benzoxazepine, and benzoxazocine from a common synthetic intermediate was established. Benzoxacycles are privileged structures in medicinal chemistry and have featured in several clinically used drugs. The synthesis of a benzofuran containing an aryl substituent was accomplished using potassium carbonate and sodium hydride. The one-pot synthesis of coumarin was also carried out using trans-decalin as the solvent. The optimized conditions for the one-pot synthesis of benzoxazepine can also be applied to the synthesis of benzoxazocine.

  DOI：

  10.3987/com-17-13791

文献信息

• Total Synthesis of (−)-Vindorosine
  作者：Wen Chen、Xiao-Dong Yang、Wen-Yun Tan、Xiang-Yang Zhang、Xia-Li Liao、Hongbin Zhang

  DOI：10.1002/anie.201707249

  日期：2017.9.25

  scalable synthesis of (−)‐vindorosine based on two key transformations. A highly diastereoselective vinylogous Mannich addition of dioxinone‐derived lithium dienolates with indolyl N‐tert‐butanesulfinyl imines has been developed. In addition, an intramolecular Heathcock/aza‐Prins cyclization was introduced to construct both the C, and the highly substituted E rings for the synthesis of (−)‐vindorosine

  本文概述了基于两个关键转换的（-）-vindorosine的新颖且可扩展的合成方法。已开发出一种高度非对映选择性的乙烯基二甘氨酸，二恶英酮衍生的二烯酸锂与吲哚基N-叔丁烷亚磺酰基亚胺。此外，引入了分子内Heathcock / Aza-Prins环化反应以构建C环和高度取代的E环，以合成（-）-vindorosine和相关生物碱。
• Synthesis of Highly Functionalized Pyridines: A Metal-Free Cascade Process
  作者：Kai Wei、Yu-Cui Sun、Rui Li、Jing-Feng Zhao、Wen Chen、Hongbin Zhang

  DOI：10.1021/acs.orglett.1c02234

  日期：2021.9.3

  Herein, we report a new process for the synthesis of highly functionalized pyridines based on a tandem Pummerer-type rearrangement, aza-Prins cyclization, and elimination-induced aromatization. This formal [5+1] cyclization provides pyridines in good yields with easily accessible starting materials. The synthetic potential of our new method is further demonstrated in the modification of the frameworks

  在此，我们报告了一种基于串联 Pummerer 型重排、氮杂-Prins 环化和消除诱导的芳构化合成高度官能化吡啶的新工艺。这种正式的 [5+1] 环化以良好的收率提供了易于获得的起始材料的吡啶。我们新方法的合成潜力在 BINOL 和一些天然产物的框架的修改中得到了进一步证明。
• Total synthesis of (−)-vindoline
  作者：Wen Chen、Hongchang Tian、Wenyun Tan、Xiaotong Liu、Xiaodong Yang、Hongbin Zhang

  DOI：10.1016/j.tet.2018.11.046

  日期：2019.3

  In this full paper, a stereocontrolled strategy for the total synthesis of (−)-vindoline is described. This synthetic route features: 1) rapid construction of the stereochemical center at C19 through a highly diastereoselective vinylogous Mannich addition; 2) tandem Heathcock/aza-Prins cyclization to install rings C and E in vindoline; 3) oxidative transformation of β-ketoester to enone; 4) stereoselective

  在这篇全文中，描述了用于（-）-长春新碱全合成的立体控制策略。该合成路线的特点是：1）通过高度非对映选择性的乙烯基曼尼希添加物，在C19处快速建立立体化学中心；2）串联希思考克/氮杂-普林斯环化反应，将环C和E安装在Vindoline中；3）将β-酮酸酯氧化转化为烯酮；4）用三苯基膦和四溴化碳，然后用布朗斯台德酸对C4立体化学进行立体选择性转化。
• Baker’s Yeast Mediated Bioreduction of Prochiral Ketones Having 6-(4-Oxo-1,3-dioxinyl) Group
  作者：Jun-ichi Sakaki、Miwako Suzuki、Satoshi Kobayashi、Masayuki Sato、Chikara Kaneko

  DOI：10.1246/cl.1990.901

  日期：1990.6

  Prochiral ketones having 6-(4-oxo-1,3-dioxinyl) group as one terminal unit by fermenting baker’s yeast gave chiral alcohols, which could be convertible to optically active hydroxyesters, β-ketoesters, and lactones.

  通过发酵酵母的方式，具有6-(4-氧代-1,3-二噁烯基)基团作为一个末端单元的拟手性酮类化合物得到了手性醇，这些手性醇可以转化为光学活性的羟基酯、β-酮酯和内酯。
• Regioselective Oxygenations of <i>S</i>-<i>Trans</i> Dienes, Silyl Dienol Ethers (SDEs), by Triphenyl Phosphite Ozonide (TPPO) and Its Mechanistic Study
  作者：Atsushi Mori、Manabu Abe、Masatomo Nojima

  DOI：10.1021/jo015562v

  日期：2001.5.1

  The direct oxygenation of s-trans dienes, silyl dienol ethers (SDEs) 2, by triphenyl phosphite ozonide (TPPO) has been examined in detail. The regioselective oxygenation was found to give hydroperoxide 3, alcohol 4, ketone 5, dimer 6, and peroxy phosphate 7 with concomitant formation of triphenyl phosphate 8 and diphenyl trimethylsilyl phosphate 10. The formation of peroxy phosphate 7 was found for

  已详细研究了亚磷酸三苯酯（TPPO）对s-反式二烯，甲硅烷基二烯醚（SDEs）2的直接氧化。发现区域选择性氧化产生氢过氧化物3，醇4，酮5，二聚体6和过氧磷酸盐7，同时形成磷酸三苯酯8和二苯基三甲基甲硅烷基磷酸酯10。在TPPO中首次发现过氧磷酸酯7的形成。氧化反应。低温（31）P和（1）H NMR光谱分析证明SDE与TPPO的直接反应而不会产生单线态氧。通过两性离子ZI的干预可以合理地解释含氧产物3-7的形成，该两性离子ZI可以通过SDE对臭氧化物的中心氧的亲核攻击而形成。